CN1328001C - Laser machining method - Google Patents
Laser machining method Download PDFInfo
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- CN1328001C CN1328001C CNB038052245A CN03805224A CN1328001C CN 1328001 C CN1328001 C CN 1328001C CN B038052245 A CNB038052245 A CN B038052245A CN 03805224 A CN03805224 A CN 03805224A CN 1328001 C CN1328001 C CN 1328001C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/38—Removing material by boring or cutting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/062—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam
- B23K26/0622—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses
- B23K26/0624—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses using ultrashort pulses, i.e. pulses of 1ns or less
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/36—Removing material
- B23K26/38—Removing material by boring or cutting
- B23K26/382—Removing material by boring or cutting by boring
- B23K26/389—Removing material by boring or cutting by boring of fluid openings, e.g. nozzles, jets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/36—Electric or electronic devices
- B23K2101/42—Printed circuits
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
- H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material
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- Engineering & Computer Science (AREA)
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- Laser Beam Processing (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种激光加工方法,用于在介电衬底上快速钻出小孔。The invention relates to a laser processing method for rapidly drilling small holes on a dielectric substrate.
背景技术Background technique
通过激光射线进行材料加工由于激光技术的迅速发展在最近几年已经具有越来越重要的意义。尤其是对电子产品加工领域由于结构部件越来越微型化电路板以及衬底的激光加工已经成为不可放弃的工具,一般能够根据结构部件的微型化实现所需的结构部件和/或衬底的微型化。例如可以在衬底上钻出小孔,它具有比常见的钻头钻出的小孔直径相比更小的直径。前提是,精确地已知在衬底上产生的激光射线的激光功率,此外也可以钻出通孔或所谓的盲孔,盲孔对于多层电路板尤其是重要的,因为通过后面的盲孔金属化可以使多层电路板的不同金属层相互间导电连接并因此可以明显地提高在衬底上的集成密度。Material processing by means of laser beams has become increasingly important in recent years due to the rapid development of laser technology. Especially in the field of electronic product processing, laser processing of circuit boards and substrates has become an indispensable tool due to the increasingly miniaturized structural components. Generally, the required structural components and/or substrates can be realized according to the miniaturization of structural components. miniaturization. For example, small holes can be drilled in the substrate, which have a smaller diameter than the diameter of small holes drilled by conventional drills. The precondition is that the laser power of the laser beam generated on the substrate is known precisely. In addition, through-holes or so-called blind holes can also be drilled. Blind holes are especially important for multilayer circuit boards, because through The metallization can electrically connect the different metal layers of the multilayer printed circuit board to one another and thus significantly increase the integration density on the substrate.
由US 5,593,606已知一种激光加工装置,通过它可以在多层衬底上钻出直径在50至200μm之间的小孔。作为激光光源使用一个连续泵汲的品质良好的Nd:YAG激光器,它按照一个频率转换产生在紫外光谱区的激光脉冲。各激光脉冲具有一个约250mW的平均脉冲功率和数量级为100ns的脉冲长度。由此各脉冲得到一个非常微小的约25nJ的能量,使得为了钻出一个孔必需使用许多激光脉冲。此外因为脉冲重复频率被限定在几kHz,产量、即单位时间钻出的小孔数量相应地很少,因此通过这种激光加工装置根据材料和要被钻孔的层厚每单位时间只能钻出相对很少的小孔。A laser processing device is known from US 5,593,606, by means of which small holes with a diameter between 50 and 200 μm can be drilled in multilayer substrates. A continuously pumped good-quality Nd:YAG laser is used as laser light source, which generates laser pulses in the ultraviolet spectral region according to a frequency conversion. Each laser pulse has an average pulse power of approximately 250 mW and a pulse length of the order of 100 ns. Each pulse thus yields a very small energy of about 25 nJ, so that many laser pulses must be used to drill a hole. In addition, because the pulse repetition frequency is limited to a few kHz, the throughput, that is, the number of small holes drilled per unit time is correspondingly small, so only one per unit time can be drilled with this laser processing device depending on the material and the layer thickness to be drilled. relatively few pinholes.
此外已知,用于材料加工和尤其是用于在衬底上钻出小孔可以使用波长为9.2-10.6μm的CO2激光器或基准波长为1064nm的脉冲固体激光器,例如Nd:YAG激光器或Nd:YVO4激光器。使用这种在红外光谱区获得的常见的CO2激光源存在缺陷,所产生的激光脉冲的脉冲长度是相对较长的μs数量级。由此使要被加工的衬底处于较高的热负荷下,使得钻出的小孔的几何形状由于钻孔毛刺或由于在孔边缘上的淀积明显偏离最佳的(圆柱形或圆柱形)形状并由此降低了钻出小孔的质量。淀积例如由固化的蒸汽物产生,这种蒸汽物由于激光射线的加热使衬底材料升华而产生。但是淀积也可能由于固体衬底材料的小颗粒产生,这些颗粒由于剧烈地不均匀的衬底加热而被抛在孔边缘上。It is also known that for material processing and especially for drilling small holes in substrates CO2 lasers with a wavelength of 9.2-10.6 μm or pulsed solid-state lasers with a reference wavelength of 1064 nm, such as Nd:YAG lasers or Nd : YVO 4 laser. The drawback of using such common CO2 laser sources obtained in the infrared spectral region is that the pulse length of the generated laser pulses is relatively long in the order of μs. This puts the substrate to be processed under high thermal load, so that the geometry of the drilled holes deviates significantly from the optimum (cylindrical or cylindrical shape) due to drilling burrs or due to deposits on the edge of the hole. ) shape and thus reduces the quality of the drilled hole. The deposition occurs, for example, from solidified vapors which sublimate the substrate material due to the heating of the laser beam. However, deposition can also occur due to small particles of solid substrate material which are thrown onto the hole edges due to the strongly uneven heating of the substrate.
由DE 100 20 559已知一种通过在可见光或在靠近红外的光谱区里的超短激光脉冲加工材料的方法。在此通过一个激光源产生脉冲长度小于300ps且重复率在100kHz至1GHz的激光脉冲。各激光脉冲的强度被总共产生的激光脉冲在一个光学放大器中放大。被放大的激光脉冲具有小于300ps的脉冲长度和1Hz至1MHz的重复率,该激光脉冲用于材料加工。未放大的同样指向要被加工材料的脉冲用于检查要被加工的材料。作为检查方法例如产生所谓的光学相干X照相术。From DE 100 20 559 a method is known for processing materials by means of ultrashort laser pulses in the visible or near infrared spectral region. In this case, laser pulses with a pulse length of less than 300 ps and a repetition rate of 100 kHz to 1 GHz are generated by a laser source. The intensity of the individual laser pulses is amplified by the total generated laser pulses in an optical amplifier. The amplified laser pulse has a pulse length of less than 300 ps and a repetition rate of 1 Hz to 1 MHz, which is used for material processing. The unamplified pulses, which are also directed towards the material to be processed, are used for checking the material to be processed. For example, so-called optical coherence radiography is used as an inspection method.
发明内容Contents of the invention
本发明的目的是,提出一种用于在介电衬底上钻出小孔的方法,其中在短时间内能够钻出大量高质量的小孔。The object of the present invention is to propose a method for drilling small holes in a dielectric substrate, in which a large number of high-quality small holes can be drilled in a short time.
本发明的技术方案是提供一种用于在介电衬底上快速钻孔的激光加工方法,作为激光源使用一个高品质的CO2激光器,它产生一个脉冲的激光射线,该激光射线具有大于50kHz的脉冲重复频率,短于200ns的脉冲长度和每个激光脉冲至少10-4焦耳的能量,所述激光射线通过一个偏转单元偏转到要被加工的衬底上。The technical solution of the present invention is to provide a kind of laser processing method that is used for fast drilling on the dielectric substrate, uses a high-quality CO2laser as laser source, and it produces a pulsed laser beam, and this laser beam has more than With a pulse repetition frequency of 50 kHz, a pulse length shorter than 200 ns and an energy of at least 10 −4 Joules per laser pulse, the laser beam is deflected by a deflection unit onto the substrate to be processed.
本发明的基本构思在于,对于适合的参数,即波长、脉冲长度、重复率和用于加工的激光射线的脉冲能量不仅可以提高产量、即单位时间内钻出小孔的数量而且可以改善所得到的孔质量。按照本发明为了产生脉冲的激光射线使用一个高品质的CO2激光器。CO2激光器的高品质开关可以通过一个所谓的声电(akustooptisch)开关实现。例如一个CdTe晶体适合于此,它通过一个兆赫区频率的机械振荡激励。The basic idea of the invention is that, with suitable parameters, namely wavelength, pulse length, repetition rate and pulse energy of the laser beam used for processing, not only the throughput, i.e. the number of small holes drilled per unit time, but also the resulting hole quality. According to the invention, a high-quality CO 2 laser is used for generating the pulsed laser beam. High-quality switching of CO2 lasers can be achieved with a so-called acoustooptisch switch. For example, a CdTe crystal is suitable for this, which is excited by a mechanical oscillation at a frequency in the megahertz region.
当由激光源发出的激光射线在自身的聚焦镜头前通过一个射线扩径扩大时,按照权利要求4的所加工的激光射线尤其可以聚焦到50至200μm直径上。对此要指出,应用射线扩径的结果是被加工的激光射线具有更微小的焦深,因此必需以尽可能高的精度保持聚焦镜头与要被加工的物体表面之间的距离。通过这种方法可以避免所钻出的小孔存在不期望的扩径或锥形几何形状。The processed laser beam according to claim 4 can in particular be focused to a diameter of 50 to 200 μm, if the laser beam emitted by the laser source is enlarged by a beam expander in front of its own focusing lens. In this regard, it should be pointed out that the use of beam expansion results in a smaller depth of focus of the processed laser beam, so that the distance between the focusing lens and the surface of the object to be processed must be maintained with the highest possible precision. In this way, undesired widening or conical geometries of the drilled holes can be avoided.
钻盲孔尤其用于多层衬底的加工。Drilling blind vias is especially used in the processing of multilayer substrates.
根据衬底材料和厚度或要被钻孔的深度或者通过唯一的激光脉冲或者通过前后衔接地激光脉冲对准被加工物体进行钻孔。在使用连续的多个激光脉冲时要注意,为了避免不好的钻孔质量各激光脉冲尽可能在物体的相同位置上产生。对于已经进行的实验已经证实,为此所需的聚焦面在空间上的重叠要保持至少66%。Depending on the substrate material and thickness or the depth to be drilled, the holes are drilled either by a single laser pulse or by consecutive laser pulses directed at the object to be processed. When using several laser pulses in succession, care must be taken that the individual laser pulses are generated as far as possible at the same position on the object in order to avoid poor drilling quality. Experiments already carried out have shown that the spatial overlap of the focal planes required for this remains at least 66%.
用于加工由LCP( Liquid Cristalline Polymer)即液晶聚合物衬底材料制成的衬底最好使用长度最大为150ns的脉冲,这种衬底材料具有直达40GHz的突出的电特性并且它不仅不透水份、氧气而且也不透其它气体和液体。It is best to use pulses with a length of up to 150ns for processing substrates made of LCP ( Liquid Cristalline Polymer ), that is, liquid crystal polymer substrate materials. This substrate material has outstanding electrical properties up to 40GHz and it Not only impermeable to water, oxygen but also other gases and liquids.
为了加工通过玻璃纤维材料机械强化的介电衬底FR4(FlameRetard 4),例如ISOLA公司的材料C-1080,按照权利要求8至少50kHz的脉冲重复频率是适合的,并且尤其优选60kHz至100kHz的脉冲重复频率。For the processing of dielectric substrates FR4 (FlameRetard 4) mechanically reinforced by glass fiber materials, such as the material C-1080 of the company ISOLA, a pulse repetition frequency of at least 50 kHz is suitable according to claim 8, and pulses of 60 kHz to 100 kHz are especially preferred repeat frequency.
附图说明Description of drawings
本发明的其它优点和特征由下面对目前优选的实施例的示例性描述给出。在附图中Further advantages and features of the invention emerge from the following exemplary description of presently preferred embodiments. in the attached picture
图1以示意图示出透穿衬底钻孔,Figure 1 schematically shows through-substrate drilling,
图2以图表示出与所使用的LCP衬底厚度有关的最大可达到的钻孔生产量。FIG. 2 graphically shows the maximum achievable drilling throughput as a function of the thickness of the LCP substrate used.
具体实施方式Detailed ways
按照在图1中所示的本发明的实施例钻孔通过一个激光加工装置由此实现,一个由未示出CO2激光器发出的波长为9.2±0.2μm的激光射线通过一个射线扩径器1这样扩径,使激光射线的直径与激光射线在激光的输出耦合反射镜上的直径相比放大系数1.5至2。扩径的激光射线通过一个偏转单元2偏转90°,该偏转单元包括至少两个未示出的活动镜。偏转的激光射线通过一个远心的聚焦镜头3这样聚焦,使一个激光射线以100μm至200μm的有效聚焦直径对准要被加工的物体,该物体按照在此所示的实施例是一个单层衬底6。所述偏转单元2的两个反射镜这样设置,使激光射线4可以在短时间内在给定区域内部的任意位置对准衬底6的表面。According to the embodiment of the invention shown in Fig. 1, the drilling is realized by a laser processing device, and a laser beam with a wavelength of 9.2 ± 0.2 μm emitted by a not shown CO2 laser passes through a beam expander 1 The diameter is expanded in such a way that the diameter of the laser beam is multiplied by a factor of 1.5 to 2 compared to the diameter of the laser beam at the output coupling mirror of the laser. The enlarged laser beam is deflected by 90° by a deflection unit 2 comprising at least two movable mirrors (not shown). The deflected laser beam is focused by a telecentric focusing lens 3 in such a way that a laser beam with an effective focus diameter of 100 μm to 200 μm is aimed at the object to be processed, which according to the exemplary embodiment shown here is a single-layer substrate Bottom 6. The two mirrors of the deflection unit 2 are arranged in such a way that the laser beam 4 can be aimed at the surface of the substrate 6 at any position within a given area within a short time.
所述衬底6由LCP材料制成。这种材料例如由Ticona公司的Vectra H840或Dupont de Nemours公司的Zenite 7738提供。但是要指出,对于衬底也可以使用其它的介电材料,如FR4或环氧材料RCC。The substrate 6 is made of LCP material. Such materials are offered, for example, as Vectra H840 from the company Ticona or Zenite 7738 from the company Dupont de Nemours. It is to be pointed out, however, that other dielectric materials such as FR4 or epoxy RCC can also be used for the substrate.
由未示出的高品质CO2激光源产生的激光射线4发出重复频率至少为50kHz的激光脉冲,它具有小于150ns的脉冲长度和至少0.7mJ的脉冲能量。在要被加工的衬底6上产生的激光射线4的直径为100μm至200μm。通过这种方法钻出直径为120μm至250μm的小孔5,其中所产生的孔质量与通过常见激光加工装置钻出的小孔相比得到明显地改善。The laser beam 4 produced by a not shown high-quality CO2 laser source emits laser pulses with a repetition rate of at least 50 kHz, which have a pulse length of less than 150 ns and a pulse energy of at least 0.7 mJ. The diameter of the laser beam 4 generated on the substrate 6 to be processed is 100 μm to 200 μm. Small holes 5 with a diameter of 120 μm to 250 μm are drilled in this way, the quality of the resulting holes being significantly improved compared to small holes drilled with conventional laser processing devices.
还要指出,为了达到高的钻孔生产量必需这样构成成像单元2,使偏转到要被加工衬底6上的激光射线4可以麻利地从一个尽可能精确定义的衬底表面上的位置偏转到另一个同样尽可能精确定义的衬底表面的位置上。因此在使用这种快速偏转单元2时由于相对较大的脉冲能量,由于短的脉冲长度和所使用的激光射线4的波长不仅实现高的钻孔生产量而且使衬底材料的热负荷最小并由此避免围绕钻出孔的钻孔毛刺或淀积。It should also be pointed out that in order to achieve a high drilling throughput it is necessary to configure the imaging unit 2 in such a way that the laser beam 4 deflected onto the substrate 6 to be processed can be deflected easily from a position on the substrate surface as precisely defined as possible. to another position on the substrate surface that is also defined as precisely as possible. Therefore, when using such a fast deflection unit 2, due to the relatively high pulse energy, due to the short pulse length and the wavelength of the laser beam 4 used, not only a high drilling throughput is achieved, but also the thermal load on the substrate material is minimized and Drilling burrs or deposits around the drilled holes are thereby avoided.
图2示出一个实验结果,其中图解地示出与衬底厚度相关地能够以高的钻孔质量所钻出的最大钻孔数量。在此在水平座标上厚度d的单位为毫米(mm)。在纵坐标上给出每秒钟钻出的钻孔生产量N/t。所使用的衬底仍然由LCP材料制成。要被钻孔的LCP衬底越薄,钻孔的生产量就越高。对于0.5mm的厚度每秒可以钻出300个孔。对于0.4mm的厚度能够以相同质量钻出的孔的数量可以提高到每秒500个。在厚度为0.15mm时钻出孔的生产量提高到每秒1250个孔。FIG. 2 shows the results of an experiment in which the maximum number of boreholes that can be drilled with high borehole quality is shown diagrammatically as a function of the substrate thickness. Here, the unit of the thickness d on the horizontal coordinate is millimeter (mm). The throughput N/t of boreholes drilled per second is given on the ordinate. The substrate used is still made of LCP material. The thinner the LCP substrate to be drilled, the higher the drilling throughput. 300 holes can be drilled per second for a thickness of 0.5mm. The number of holes that can be drilled with the same quality can be increased to 500 per second for a thickness of 0.4 mm. The throughput of drilled holes increased to 1250 holes per second at a thickness of 0.15mm.
还要指出,在电子产品加工中经常使用由所谓注塑衬底构成的0.4mm的LCP衬底,因此每秒500个钻出孔的生产量与通过常见的激光加工设备可以达到的生产量相比明显增加。It should also be pointed out that 0.4 mm LCP substrates consisting of so-called injection-molded substrates are frequently used in electronics processing, so that the throughput of 500 drilled holes per second is compared with the throughput achievable with conventional laser processing equipment obviously increase.
总之本发明实现一个用于在介电衬底6上快速钻出小孔的激光加工方法。作为激光源使用一个高品质的CO2激光器,它可以产生一个脉冲的激光射线4,它具有大于50kHz的脉冲重复频率,脉冲长度短于200ns而每个激光脉冲的能量至少为10-4焦耳。通过偏转单元使激光脉冲4偏转到要被加工的衬底6上。通过上述表征激光射线4的参数不仅可以保证高的钻出孔5生产量而且可以保证高的钻孔质量。因此可以在0.4mm厚的LCP衬底上每秒钻出500个小孔,其中钻出孔的几何形状近似圆柱形或近似圆锥形。所选择的波长、短脉冲长度、高重复频率和与常见的激光加工装置相比在电子产品加工领域中高的脉冲能量的结果是在实现高的生产量的同时实现高的钻孔质量。Overall, the invention implements a laser processing method for rapidly drilling small holes in a dielectric substrate 6 . As the laser source use a high-quality CO2 laser that can generate a pulsed laser ray 4 with a pulse repetition rate greater than 50 kHz, a pulse length shorter than 200 ns and an energy of at least 10-4 joules per laser pulse. The laser pulse 4 is deflected by the deflection unit onto the substrate 6 to be processed. By means of the above-mentioned parameters characterizing the laser beam 4 , not only a high throughput of drilled holes 5 but also a high drilling quality can be guaranteed. Therefore, 500 small holes can be drilled per second on a 0.4 mm thick LCP substrate, wherein the geometry of the drilled holes is approximately cylindrical or approximately conical. The selected wavelengths, short pulse lengths, high repetition rates and, compared to conventional laser processing devices, high pulse energies in the field of electronics processing result in high drilling quality at the same time as high throughput is achieved.
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| DE10209617A DE10209617C1 (en) | 2002-03-05 | 2002-03-05 | Laser processing method, for rapidly boring holes in dielectric substrates, comprises deviating a laser beam produced by a carbon dioxide laser onto the substrate to be processed using a deviating unit |
| DE10209617.1 | 2002-03-05 |
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| ES2302418B1 (en) * | 2005-12-21 | 2009-05-08 | Universidad De Cadiz | LASER MACHINING METHOD OF EPOXI RESIN COMPOSITE MATERIALS REINFORCED WITH CARBON FIBERS. |
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| US8237080B2 (en) * | 2008-03-27 | 2012-08-07 | Electro Scientific Industries, Inc | Method and apparatus for laser drilling holes with Gaussian pulses |
| CN101829850A (en) * | 2010-04-01 | 2010-09-15 | 深圳市大族激光科技股份有限公司 | Method for processing blind hole |
| EP2658674B1 (en) | 2010-12-30 | 2017-03-01 | 3M Innovative Properties Company | Apparatus for laser converting using a support member having a gold facing layer; method of laser converting a sheet material using such apparatus |
| WO2012092478A1 (en) | 2010-12-30 | 2012-07-05 | 3M Innovative Properties Company | Laser cutting method and articles produced therewith |
| CN103252587A (en) * | 2013-04-27 | 2013-08-21 | 北京工业大学 | Glass surface blind hole processing method |
| CN103240531B (en) * | 2013-05-10 | 2015-02-11 | 中国电子科技集团公司第五十四研究所 | Segmentation laser punching method |
| CN105081564B (en) * | 2015-08-31 | 2017-03-29 | 大族激光科技产业集团股份有限公司 | The processing method in shape hole in a kind of strengthens glass |
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| CN113369719B (en) * | 2021-05-14 | 2023-01-31 | 惠州中京电子科技有限公司 | Laser drilling method for LED carrier plate |
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| KR20040083546A (en) | 2004-10-02 |
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| WO2003074224A1 (en) | 2003-09-12 |
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| US6833528B2 (en) | 2004-12-21 |
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